Substituted phthalocyanine dye developers and their use in multicolor diffusion transfer processes

ABSTRACT

Novel phthalocyanine dye developers (phthalocyanine dyes which are also silver halide developing agents) and also to photographic systems employing the same.

United States Patent [191 Idelson [4 Dec. 31, 1974 SUBSTITUTED PHTHALOCYANINE DYE DEVELOPERS AND THEIR USE IN MULTICOLOR DIFFUSION TRANSFER PROCESSES [75] Inventor: Elbert M. Idelson, Newton Lower Falls, Mass.

[73] Assignee: Polaroid Corporation, Cambridge,

Mass.

[22] Filed: June 21, 1973 [21] Appl. No.: 372,268

Related US. Application Data [60] Continuation of Ser. No. 851,525, June 30, 1969, abandoned, which is a division of Ser. No. 694,167, Dec. 28, 1967, Pat. No. 3,482,972.

Primary Examiner-Harry l. Moatz Attorney, Agent, or Firm-John P. Morley [5 7 ABSTRACT Novel phthalocyanine dye developers (phthalocyanine dyes which are also silver halide developing agents) and also to photographic systems employing the same.

7 Claims, No Drawings 1 SUBSTITUTED PHTI-IALOCYANINE DYE DEVELOPERS AND THEIR USE IN MULTICOLOR DIFFUSION TRANSFER PROCESSES CROSS REFERENCE TO RELATED PATENT APPLICATIONS BACKGROUND OF THE INVENTION It is one object of the present invention to provide novel processes, products and compositions for the development of silver halide emulsions, in which novel colored silver halide developing agents are used to develop a latent photographic image.

Another object is to provide novel systems forthe development of'silver halide emulsions, in which colored developing agents develop a photographic latent image and impart a reversed or positive colored image of said latent image to a superposed image-receiving element.

A further object of this invention is to provide a novel class of compounds useful in photographic products, processes and compositions such as described and claimed in U.S. Pat. No. 2,983,606, issued to Howard G. Rogers.

A further object is to provide novel products and processes suitable for use in preparing monochromatic and multichromatic photographic images.

Another object is to provide a novel class of phthalocyanine dyes which are also silver halide developing agents.

Still another object is to provide a'cyan dye developer whose photographic images are of superior color.

Other objects of the invention will in part be obvious and will in part appear hereinafter.

The invention accordingly comprises the processes involving the several steps and the relation and order of one or more of such steps with respect to each of the others and the products possessing the features, prop erties and the relation of components which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.

The novel photographic developing agents of this invention possess the properties of both a dye and a silver halide developing agent; thus they may be referred to as dye developers. The nature of these dye developers will be described hereinafter.

The photographic processes and compositions disclosed herein are particularly useful in the treatment of a latent image present in a photosensitive element, such as an exposed silver halide emulsion, whereby a positive dye image thereof may be imparted to another element, herein referred to as an image-carrying or imagereceiving element.

U.S. Pat. No. 2,983,606, issued May 9, l96'l to Howard 0. Rogers, discloses diffusion transfer processes wherein a photographic negative material, such as a photographic element comprising an exposed silver halide emulsion, is developed in the presence of a dye developer to impart to an image-receiving layer a reversed or positive dye image of the developed image by permeating into said emulsion layer a suitable liquid processing composition and bringing said emulsion 2 It is an object of this invention to provide additional dye developers which give rise to transfer images of superior color characteristics and are suitable for use in such processes. The dye developers of this invention provide monochrome images of green. cyan and blue colors.

In carrying out the process of this invention, a photosensitive element containing a silver halide emulsion is exposed and wetted with a liquid processing composition, for example, by immersing, coating, spraying, flowing, etc., in thedark, and the photosensitive element superposed,'prior to, during or after wetting, on an image-receiving element. ln a preferred embodiment, the photosensitive element contains a layer of dye developer, and the liquid processing composition is applied to the photosensitive element in a uniform layer as the photosensitive element is brought into sulayer into superposed relationship with an appropriate si t alayer perposed position with an image-receiving element. The liquid processing composition permeates the emulsion to provide a solution of dye developer substantially uniformly distributed therein. As the exposed silver halide emulsion is developed,the oxidation product of the dye developer is immobilized or precipitated in situ with the developed silver, thereby providing an imagewise distribution of unoxidized dye developer dissolved in the liquid processing composition. This immobilization is apparently, at least in part, due to a change in the solubility characteristics of the dye'developer upon oxidation, and especially as regards its solubility in al-, kaline solutions. It also may be due, in part, to a tanning effect on the emulsion by the oxidized developing agent. At least part of this imagewise distribution of unoxidized dye' developer is transferred, by imbibition, to a superposed image-receiving layer. Under certain circumstances, the layer of the liquid processing composition may be utilized as the image-receiving layer. The image-receiving layer receives a depthwise diffusion, from the emulsion, of unoxidized dye developer, without appreciably disturbing the imagewise distribution thereof, to provide a reversed or. positive, colored image of the developed image. The image-receiving element may contain agents adapted to mordant or otherwise. fix the diffused, unoxidized dye developer. If the color of the diffused dye developer is affected by changes in the pH of the image-receiving element, this pH may be adjusted'in accordance with well-known techniques to provide a pH affording the desired color. Imbibition periods of approximately one minute have been found to give good results, but this contact period may be adjusted where necessary to compensate for variations in temperature or other conditions. The desired positive image is revealed by stripping the imagereceiving element from the photosensitive element at the end of the imbibition period.

The dye developers of this invention may be utilized in the photosensitive element, for example, in, on or behind the silver halide emulsion, or they may be utilized in the image-receiving element or in the liquid processing composition. In a preferred embodiment, a A

coating or layer of the dye developer is placed behind the silver halide emulsion, i.e., on the side of the emulsion adapted to be located most distant from the photographed subject when the emulsion is exposed and preferably also adapted to be most distant from the image-receiving element when in superposed relationship therewith. ln this preferred embodiment, the layer of dye developer may be applied by using a coating solution containing about 0.5 to 8 percent by weight of the dye develgper Similar concentrations may be used if the dye developer is utilized as a component of the liquid processing composition. In an especially useful mode of dispersing the dye developers in the photosensitive elements, the dye developer is dispersed in an alkaline solution permeable polymeric matrix wherein the mean particle size distribution of at least 50 percent and preferably at least 75 percent of the dye is below one micron in diameter. Reference is made to the copending application of Howard G. Rogers and Sidney Kasman, Ser. No. 659,370, filed Aug. 9, 1967.

The liquid processing composition above referred to comprises at least an aqueous solution of an alkaline compound, for example, diethylamine, sodium hydroxide or sodium carbonate, and may contain the dye developer. In some instances, it may contain a minor amount of a conventional developing agent. if the liquid processing composition is to be applied to the emulsion by being spread thereon, preferably in a relatively thin, uniform layer, it may also include a viscosityincreasing compound constituting the film-forming material of the type which, when said composition is spread and dried, will form a relatively firm and relatively stable film. A preferred film-forming material is a high molecular weight polymer such as apolymeric, water-soluble ether inert to an alkali solution, as, for example, a hydroxyethyl cellulose or sodium carboxymethyl cellulose. Other film-forming materials or thickening agents whose ability to increase viscosity is substantially unaffected when left in solution for a long period of time may also be used.

The novel dye developers of this invention may be defined as phthalocyanines, or nuclear substituted derivatives thereof, containing at least one substituent comprising a disubstitutedphenyl silver halide developing radical linked to a phthalocyanine nucleus directly, or indirectly, through an appropriate divalent linking group in the manner known heretofore in the dye developer art. The phthalocyanines can be used in the metal-free form or in the form of complexes with metals known to form phthalocyanine complexes.

The term disubstitutedphenyl silver halide developing radical is intended to include dihydroxyphenyl, aminophenol, and diaminophenyl silver halide developing radicals, wherein the hydroxyl and/or amino groups present are situated ortho or para to each other.

The terms phthalocyanine(s) when used alone as either a noun or an adjective is intended to refer to both metallo and non-metallo phthalocyanine compounds.

The novel dye developers of this invention which contain a central metal atom can be illustrated by the wherein it is provided that of the 16 R substituents present on the phthalocyanine ring at least one and no more than four are as R groups, there being no more than two R on any one benzene ring. the remaining R substituents being R groups, wherein R comprises a group (-A),,-E; A is a divalent organic linking radical; n is a number of from O to l inclusive; E is an aryl group selected from the group consisting of benzene and naphthalene radicals so substituted by at least two groups selected from the group consisting of hydroxyl and amino groups which are situated ortho or para to each other as to be capable of developing an exposed silver halide photographic emulsion; M is a metal selected from the group consisting of cobalt, nickel, copper, chromium, magnesium and zinc; and each R comprises the same or a different moiety selected from the group consisting of monovalent organic and monovalent inorganic radicals, neither of which contain a silver halide developing radical, and hydrogen. Typical examples of R moieties include: SO H, Br, -NH CH Cl, and SO NH Reference is made to Chapter 5 of Moser and Thomas, Phthalocyanine Compounds, Reinhold, Copyright 1963.

The novel dye developers of this invention which do not contain a central metal atom can be illustrated by the following formula:

wherein it is provided that of the 16 R substituents present on the phthalocyanine ring, at least one and no more than four are as R groups, with not more than two R groups being on any one benzene ring, the remaining R substituents being R groups, wherein R, R A, E and n are of the significance indicated at formula (A).

One preferred class of dye developers within formula (A) comprises the compounds wherein the linking group between the phthalocyanine nucleus and a disubstituted phenyl silver halide developing radical is wherein X and D are as defined indicated below.

Such compounds are represented by the formula:

' hydrogen.

wherein it is provided that of the 16 R substituents present on the phthalocyanine ring at least one and no more than four are as R groups, there being no more than two R groups on any one benzene ring, the remaining R substituents being R groups, wherein R is 20 X is H or an alkyl group of 1-6 carbon atoms inclusive;

Within this preferred class of dye developers there is a more preferred class of dye developers wherein X is hydrogen or methyl and the metal is copper.

Such compounds are represented by the formula:

I www wherein it is provided that ofthe 16 R substituents present on the phthalocyanine ring at least one and no more than four are as R groups, there being no more than two R groups on any one benzene ring, the re- 6 5 6Q malnmg R SUbStltU l'itS b ll'lg R groups, wherein R is OH Xi.

X is .H or Ch and each R is the same or a different moiety selected from the group consisting of phenyl, alkyl, alkoxy, hydrogen, halogen, carboxyl and The disubstitutedphenyl silver halide developing substituents and the divalent linking groups referred to above may be selected from those heretofore wellknown in the art.

As examples of useful disubstitutedphenyl silver halide developing substituents, mention may be made of the following dihydroxyphenyl silver halide developing substituents namely, ortho-dihydroxyphenyl, paradihydroxyphenyl and nuclear-substituted derivatives thereof, e.g., chloro, methyl, phen yl, and/or methoxysubstituted derivatives thereof, particularly nuclearsubstituted p-dihydroxyphenyls such as methylhydroquinonyl, p-methylphenylhydroquinonyl, chlorohydroquinonyl, methoxyhydroquinonyl, 2,6-dimethylhydroquinonyl, 2,6-dimethoxyhydroquinonyl, 2- methoxy-6-methylhydroquinonyl, 2,3-dimethylhydroquinonyl, 2,5,6-trimethylhydroquinonyl, etc.

As examples of useful diaminophenyl and monoamino, monohydroxyphenyl silver halide developing agents, mention may be made of any of the above dihydroxy substituents wherein one or both of the hydroxyl groups is replaced by Nl-l As examples of useful divalent linking groups joining the disubstitutedphenyl moiety to the designated position on the phthalocyanine moiety, mention may be linking groups described in U.S. Pat. No. 3,288,778; aminophenalkylthio substituents such as disclosed in U.S. Pat. No. 3,009,958; aminoalkylamino substituents such as disclosed in U.S. Pat. No. 3,002,997; alkylthio substituents such as disclosed in U.S. Pat. No. 3,043,690; sminoalkyl substituents such as described in U.S. Pat. No. 3,062,884; aminophenyl substituents such as disclosed in U.S. Pat. No. 3,134,81 l; the acyl substituentsdisclosed in U.S. Pat. No. 3,142,564; the aminophenoxy substituents such as disclosed in U.S. Pat. No. 3,061,434; lower alkylene and the various other linking substituents disclosed in U.S. Pat. No. 3,255,00l, etc. Where the linking substituent is alkylene or contains an alkyl or alkylene moiety, the number of carbon atoms is preferably l-4.

One method of preparing the novel dye developers of this invention comprises reacting a compound of the formula:

C-OH

stitutedphenyl silver halide developing radical or apro- 7 8 tected derivative of said radical. The nature of the apchosen from among the 46 metals known to form a propriate treatment mentioned above will vary with the metallo phthalocyanine, with a compound such as particular Z substituent utilized. Such procedures are ClSO H, or an acyl halide, or the reaction product of seen to be within the skill of the art; The so-treated CH O HCl. These are capable of donating a substitumetallo phthalocyanine is then reacted with a com- 5 ent, Z, such as (SO Cl) or CO alkyl, or CH Cl pound which contains the disubstitutedphenyl silver upon reaction with said phthalocyanine such as to form halide developing radical or its protected derivative. A a Z-substituted phthalocyanine, suitable metal chloride for use in this process is cupric (F) chloride. The Z substituent on the compound, i.e., the [MP 12 phthalic acid, is H or a substituent which is or can be 10 rendered capable of being reactive with or replaceable by the substituentcomprising the disubstitutedphenyl silver halide developing radical to form the desired dye developer or a protected derivative thereof. Typical Z wherein n is a number of from 1 to 16 and wherein the Z substituent is defined as previously noted with reference to the Z-substituted phthalic acid. The Z- substituted phthalocyanine is appropriately treated, if necessary, such as to render the Z substituent capable substituents include SO H,

' NH of being able to react with or be replaced by the substituent comprising the disubstitutedphenyl silver halide COOH' NH?* #31121, developing radical or a protected derivative of said radical.

20 Several modes of preparing phthalocyanine compounds are set forth in detail in Phthalocyanine Compounds, Moser and Thomas, Reinhold Publishing Corporation. The compounds so prepared can be utilized Another method of preparing the novel compounds to prepare the dye developers by the process set forth of the present invention is to react an unsubstituted immediately above. preformed phthalocyanine, wherein the metallo or As examples of dye developers within the scope of non-metallo moiety of the molecule, if present, is this invention, mention may be made of:

XII.

N C C N "W w KL. HQ H H C C N XIII.

XXIV.

XXIII.

which could be written as that there are four possible isomeric forms of such a on l When each of the four benzene rings is substituted in only one position, but with a different substituent on each benzene ring, the number of isomers is increased many fold. The possible number of isomers becomes even more complex when there is more than one substituent on each benzene ring.

It is fully intended that all of the possible isomeric forms of the compounds set forth by formula within the specification and in the appended claims are to be considered within the scope of the invention.

It will also be appreciated that in addition to the various isomers that exist for the several compounds, that many of the nonsymmetrical compounds, i.e., those wherein the substituents on any of the four benzene nuclei differ, illustrate but one of a family of compounds. For example, if a mono-substituted phthalic acid is mixed with a di-substituted phthalic acid in the condensation step with the metal chloride, it is seen that the resulting metallo phthalocyanine can be all monosubstituted, all di-substituted or a part mono, part disubstituted compound.

Similarly, in the preformed phthalocyanine synthesis for these dye developers, the molar amount ofthe compound which donates the Z substituent and the reaction conditions will have a direct relation on the number of Z substituents formed on the phthalocyanine.

It is fully intended that all of the various members of the families of the several compounds are to be included within the scope of this invention.

Compounds of the same structure except for a substitution ofa different metal or a deletion of the metal and the replacement thereof by two hydrogen atoms show no substantial color change.

It is known that phthalocyanine dyes that are unsubstituted have the ability to impart a cyan color to substances. When dye developers were prepared from such compounds, it was found that the nature of the group used to link the dye portion to the developer portion of the molecule could cause a color change toward green or blue from cyan. it was found thatwhen certain moieties were used as the entire linking group or formed the part of the linking group next adjacent to the phthalocyanine ring that this shift away from cyan was not experienced, regardless of the nature of the remainder of the linking group, provided that the remainder is nonchromophoric. The moieties which did not assqtllqs l rs tiftinc ude b t are not m ted toz.

AWL- m re use It was also noted that when normally cyan nonmetallo and metallo phthalocyanine dye developers were substituted on their benzene nuclei, that the use of certain moieties as these substituents would cause a color change in the images obtained. However, moieties such as SO H, SO 'NH SO NH alkyl, 'alkyl and aryl did not cause such a color change.

On the other hand the incorporation of such moieties into the molecule of a non-cyan phthalocyanine dye developer did not cause it to provide cyan images.

Dye developers which contain these non-color influencing moieties in the manners indicated exhibit a greater absorption in the red portion of the spectrum and a lesser absorption in the green and blue portions of the spectrum than cyan anthraquinone dye developers, such as l,4-bis-(a-methyl-B-hydroquinoylethylamino)-5,8-dihydroxyanthraquinone. Reference is made to the Figure of the drawing wherein the phthalocyanine dye developer is copper phthalocyanine 3,3- ,3",3"-tetra[hydroquinonyl isopropyl, amino sulfonamide]. (See Formula VI, supra).

' in the Figure, the curves representing the reflection density comparison are based on reflection spectra readings for diffusion transfer images placed in front of a spectrophotometric beam ona commercially available recording spectrophotometer. The reference standard utilized ygsa rnagnesium carbonate block. In ac: cordance with techniques known in the a rtlrea din gs were taken on the instrument and plotted. The spectrophotometric curves were chosen such that at the wave lengths of maximum absorption for each dye, the optical densities were equal. As can be seen on the spectrophotometric curves, the two compounds have an equal optical density at their individual maximum absorption peaks. The representative instantly claimed compound shows extremely good absorption in-the 600-700 millimicron range, and lower absorption in the 380-600 millimicron range than the reference compound. Since the curve is lower in the 380600 millimicron range for the representative claimed compound, it is seen that the curve more nearly approaches a perfect cyan compound curve which would show no absorption in this range. Therefore, the color obtained from the instant compounds is a better cyan.

When the instant compounds are placed in a multicolor subtractive color environment, it is seen that bet- -ter greens and blues will result relative to anthraquinone dyes, independent of optical density.

The novel dye developers of this invention have also been found to be extremely stable against the color degradation effects of light, humidity and/or heat.

The dye developers of this invention are seen to give diffusion transfer images which show substantial improvement in color stability to actinic radiation in comparison with cyancolored azo and anthraquinone dyes of similar optical density. Reference is made to the 22 Light Stability data, infra, which compares the aforementioned anthraquinone dye developer with two phthalocyanine dye developers.

Furthermore, these dye developers are not pH sensitive and are chemically stable in an aqueous alkaline processing medium.

The invention will be illustrated in greater detail in conjunction with the following specific examples which set out representative preparation and photographic utilization of the novelcompounds of this invention. which, however, are not limited to the details therein set forth and are intended to be illustrative only.

EXAMPLE I To 42 grams of urea, heated to C., was added 42.3 grams of 4-sulfophthalic acid, said acid having been prepared by the evaporation of water from a 35 percent solution of the acid. 8 grams of copper chloride and 0.7 grams of H 80 and 0.2 grams (NH MO O 41-1 0 were also added. The mixture was heated gradually to 200 C. over a period of one hour until the urea melt became a solid mass. The mass was cooled and to this was added milliliters of' dimethyloxyphenyl]-2-methylaminopropane of the forand heated to 60-65 C. for 1 /2 hours: The mixture was then poured into a liter of dilute hydrochloric acid.

' The solid was filtered, washed with dilute hydrochloric acid anddried. '5 grams of this solid material was dissolved in 120 milliliters of methylene chloride and this solution was added slowly to 4.5 milliliters of BBr in 50 milliliters of methylene chloride. Stirring was continued for 30 minutes followed by the addition of sufficient methanol to destroy the BBr The solid was-filteredyredissolved in DMF and repr ecipitated into a liter of dilute HCl The solid was filtered, washed with dilute HCl and dried. The filter, wash and dry steps a were repeated to insure purity. etllys 9 th prq yc Theoretical ofv Experimental Cu 4.28% 4.11% N 9.98 l0.85 S 8.64 8.26 OCH; 0.78 0.00

curve of this p roduct exhibits a A at 679 in DMF, e= 155,000; and a. A at 610 millimicrons with an e of 36,600.

EXAMPLE II 10 grams of copper phthalocyanine was added to 180 grams qf chlorosulfonic acid and stirred. 20 grams of phorphorous pentachloride was added gradually to the mixture to avoid foaming. The mixture was heated to 130-135 C. for 1% to 1 /2 hours. It was then poured over crushed ice. The blue solid was filtered and dried. A sample of the blue solid was'found to be insoluble in methyl cellosolve and also in water, while the filtrate was found to be clear and almost colorless. The blue solid was copper phthalocyanine tetrasulfonyl chloride. 30 grams of this product prepared in the manner described above were dissolved in 300 milliliters of dimethyl formamide. 60 milliliters (0.03 moles) of l[2',- 5'-dimethoxyphenyl]-2-aminopropane which has the formula:

H CH3 m'elm llflz OCHa was added to the solution with stirring. The mixture was heated to about 65i5 C. for about 2 hours. At that time, the solution was cooled to room temperature and poured into 3 liters of dilute 3 normal HCl. A blue precipitate was formed. The solid was filtered, dried and redissolved in a minimal amount of hot DMF. The solid was reprecipitated by pouring this into a large excess of dilute hydrochloric acid. The solid was filtered, washed with dilute acid and dried to a blue solid.

25 milliliters (66.4 grams) of boron tribromide was added to 300 milliliters of methylene chloride. 33 grams of the blue solid product was ground to a fine powder and dissolved in 600 milliliters of methylene chloride with constant stirring. This blue solution was added dropwise into the rapidly stirring boron tribromidemethylene chloride solution. This mixture assumed a green color and a solid separated. After 2 hours of stirring, the excess boron tribromide was destroyed by the careful addition of 100 cc. of methanol. The mixture was filtered and a blue solid was isolated which was then dissolved in a minimal amount of hot DMF, and reprecipitated by pouring the solution into Experimental Theoretical Cu 4.40% 4.25% N 11.18 11.22 S 8.67 8.56 OCH; 0.17 0.00

The spectral absorption curve of this product exhibits a A at 611 millimicrons in pyridine, e= 34,600; ,..,,.68() millimicrons in DMF. s= 176,000.

It is to be seen that the amines utilized in the two processes set forth in Examples 1 and 11 above are interchangeable for each other in the two processes. When such experiments are conducted, similar results, as were obtained in Examples 1 and II, were achieved.

The novel dyes of this invention are characterized in that they contain not less than one benzenoid developing group and as such are useful dye developers. In the following example all parts are given by weight except where otherwise noted, and all operations involving light-sensitive materials are carried out in the absence of actinic radiation. These examples are intended to be illustrative only of the photographic use of the dye de velopers and should not be construed as limiting the invention in any way.

EXAMPLE 111 A photosensitive element was prepared by coating a gelatin subcoated film base at a speed of 10 feet per minute with a solution comprising 0.64 g. of copper phthalocyanine 4,4',4",4"'-tetra[hydroquinonyl isopropyl 2-methylamino sulfonamide] dissolved in 10 cc. 0f2 percent cellulose acetate hydrogen phthalate in acetone. After this coating dried, a red-sensitive silver iodobromide emulsion was coated on at a speed of 5 feet per minute and allowed to dry. This photosensitive element was exposed and processed by spreading, between the thus exposed photosensitive element and a superposed image-receiving element, an aqueous processing composition comprising:

Water cc. KOH 1 1.2 g. Hydroxyethyl cellulose 3.8 g. Benzotriazole 3.5 g. Potassium thiosulfate 0.5 g. N-benzyl-a-picolinium bromide 2.0 g. Zinc nitrate 0.5 g. Lithium nitrate 0. g.

The image-receiving element comprised baryta paper with a layer of a partial butyl ester of poly- (ethylene/maleic anhydride), followed by a layer of polyvinyl alcohol and a layer of a 2:1 mixture. by weight, of polyvinyl alcohol and poly-4-vinylpyridine. Image-receiving elements of this type are disclosed and claimed in the copending application of Edwin H. Land, Ser. No. 234,864, filed Nov. 1, 1962. After an imbibition period of approximately 1 minute, the image-receiving element was separated and contained a cyan positive image having a d of 0.26 and a d,,,,-,, of 0.14.

The same photosensitive element when processed in the same manner except with a 0.2 percent MPHQ pro cessing composition had a d of 0.20 and a d,,,,-,, of 0.1 1.

EXAMPLE IV A photosensitive element was prepared by coating a gelatin subcoated film base at a speed of 10 feet per minute with a solution comprising 0.66 g. of copper phthalocyanine 3,3',3",3"-tetra[hydroquinonyl isopropylamino sulfonamide] dissolved in 10 cc. of 2 percent cellulose acetate hydrogen phthalate in acetone. After this coating dried, a red-sensitive silver iodobromide emulsion was coated on at a speed of 5 feet per minute and allowed to dry. This photosensitive element was exposed and processed by spreading, between the thus exposed photosentitive element and a superposed image-receiving element, the aqueous processing composition set forth in Example lll, namely:

Water 100 cc. KOH 11.2 g. Hydroxycthyl cellulose 3.8 g. Benzotriazole 3. g. Potassium thiosulfate 0. g. N-benzyl-a-picolinium bromide 2.0 g. Zinc nitrate 0.5 g. Lithium nitrate 0.5 g.

The image-receiving element comprised baryta paper coated with a layer of a partial butyl ester of poly- (ethylene/maleic anhydride), followed by a layer of polyvinyl alcohol and a layer of a 2:1 mixture, by weight, of polyvinyl alcohol and poly-4-vinylpyridine. Image-receiving elements of this type are disclosed and claimed in the copending application of Edwin H. Land, Ser. No. 234,864, filed Nov. 1, 1962. After an 25 imbibition period of approximately one minute, the image-receiving element was separated and contained a cyan positive image having a d,,,.,, of 0.75 and a d,,,,-,. of 0.45.

The same photosensitive element when processed in the same manner except with a 0.2 percent 4-methylphenylhydroquinorie processing composition had a d of 0.85 and a d,,.,-, of 0.45.

The novel dye developers of this invention exhibit increased stability against the color degradation effects of actinic radiation, humidity and/or heat.

Positive dye images prepared in the manner described in Examples Ill and IV were subjected to standard accelerated fading tests and the percent of fading was noted after several dosages of radiation. The fading tests were conducted under a Xenon arc intensity of l28130 F. with infrared light filtered out at a 12 inch lamp to subject distance in the presence of 31 percent relative humidity.

The following tables illustrate the increased stability of the novel dye developers of this invention.

l.4-his-(u-methyl-fl-hydrnquinonyl-ethylaminn)-5.8dihydroxyanthraquinone (the preparation ofwhich is described in U.S. Pat. No. 3.135.606. issued to Blout cl al on June 2. H64 and in US. Pat. No. 3.209.016, issued to Blout et al on September Table II Percent Fading I 6 hours 12 hours 24 hours 48 hours Dye Developer of Example IV 9 l2 l4 l Sample ll of Control 4 l0 17 32 The control was a cyan dye developer of the formula l.4-bis-ta-methyl-B-hydroquinonyl-ethylamino)-5.8-dihydroxyanthraquinone (the preparation of which is described in U.S. Pat. No. 3.l35,606. issued to Blout et al on June 2.1964 and in U.S. Pat. No. 3.209.0l6. issued to Blout ct al on September 965% H The cyan positive images for these tests were processed with the developer composition of Examples III and IV without the addition of 4'-methylphenylhydroquinone. H

EXAMPLE V A photosensitive element was prepared by dispersing 1.0 g. of copper phthalocyanine, 3,3,3",3'-tetra (dihydroxyphenyl isopropylamino sulfonamide) in water containing percent dispersing agent, Lomar D, a sodium salt of a condensed monoaphthalene sulfonic acid, based on dye solids. This mixture was agitated by means of a Branson sonifier for one hour. An aqueous solution of 2.0 g. of 5 percent Gantrez AN-l69, (a copolymer of ethylene maleic anhydride and methyl vinyl ether), was added to this dispersion and the resulting dye dispersion was added to enough water and wetting agents to be coated on a cellulose triacetate film base at a coverage of 123.5 mg. per square foot of dye. After this coating dried, a red-sensitive silver iodobromide emulsion was coated at a coverage of 222 mg. per square foot of silver on this and allowed to dry. This photosensitive element wasexposed and processed by spreading, between the thus exposed photosensitive elernent and a superposed image-receiving element, an aqueous processing composition comprising:

Water I00 NaOH Hydroxyethyl cellulose Benzotriazole Potassium thiosulfate N-benzyla-picolinium bromide Lithium nitrate Zinc nitrate use in multicolor diffusion transfer processes. As an example of such photosensitive elements, mention may be made of the photosensitive elements disclosed and claimed in U.S. Pat. No. 3,345,163, issued Oct. 3, 1967 to Edwin H. Land and Howard G. Rogers, wherein at least two selectively sensitized photosensitive strata are superposed on a single support and are processed,.simultaneously and without separation, with a single common image-receiving element. A suitable arrangement of this type comprises a support carrying a redsensitive silver halide emulsion stratum, a greensensitive silver halide emulsion stratum and a bluesensitive silver halide emulsion stratum, said emulsions having associated therewith, respectively, a cyan dye developer, a magenta dye developer and a yellow dye developer. In one of the preferred embodiments of photo-sensitive elements of this type, the dye developers are disposed in separate alkali-permeable layers behind the photosensitive silver halide emulsion stratum with which they are associated.

The photosensitive elements within the scope of this invention may be used in roll film units which contain a plurality of photosensitive frames. The photosensitive elements of this invention are especially useful in composite roll film intended for use in a Polaroid Land Camera, or a similar camera structure such, for example, as the camera forming the subject matter of U.S. Pat. No. 2,435,717, issued to Edwin H. Land on Feb. 10, 1948. In general, such composite roll films comprise a photosensitive roll, a roll of image-receiving material and a plurality of pods containing an aqueous alkaline processing solution. The rolls and pods are so asidol); benzylaminophenol; hydroquinone; a substituted 'hydroquinone such astoluhydroquinone, phenylhydroquinone, or 4'-methylphenylhydroquinone; or a 3- pyrazolidone such as l-phenyl-3-pyrazolidorie. These silver halide developing agents are substantially colorless, at least in their unoxidized form. It is possible that some of the dye developer oxidized in exposed areas may be oxidized by an energy transfer reaction with oxidized auxiliary developing agent.

In addition, development may be effected in the presence of an onium compound, particularly a quaternary ammonium compound, in accordance with the processes disclosed and claimed in US. Pat. No. 3,173,786 issued March I6, 1965 to Milton Green and Howard G.

Rogers.

The dye developers of this invention may be used also in conventional photographic processes, such as tray or tank development of conventional photosensitive films, plates or papers to obtain black and white, monochromatic or toned prints or negatives. By way of example, a developer'composition suitable for such use may comprise an aqueous solution of approximately l-2 percent of the dye developer, 1 percent sodium hydroxide, 2 percent sodium sulfite and 0.05 percent potassium bromide. After development is completed, any unreacted dye developer is washed out of the photosensitive element, preferably with an alkaline washing medium or other medium in which the unreacted dye developer is soluble. The expression toned is used to designate photographic images wherein the silver is retained with the precipitated dye, whereas monochromatic is intended to designate dye images free of silver.

It should be noted that the dye developers of this medium are self-sufficient to provide the desired color image and do not depend upon coupling reactions to produce the desired color. They thus provide a complete departure from conventional photographic color processes in which the color is produced by a coupling reaction between a color former or coupler and the oxidized developing agent, as well as so-called autocoupling processes in which color is obtained by a reaction of the oxidized developing agent with unoxidized developing agent. a

It will be apparent that, by appropriate selection of the image-receiving element from among suitable known opaque and transparent materials, it is possible to obtain either a colored positive reflection print or a colored positive transparency. Likewise, the inventive concepts herein set forth are adaptable for multicolor work by the use of special photographic materials, for example, film materials of the type containing two or more photosensitized elements associated with an appropriate number of image-receiving elements and adapted to be treated with one or more liquid processing compositions, appropriate dye developers suitable to impart the desired subtractive colors being incorporated in the photosensitized elements or in the liquid processing compositions. Examples of such photographic materials are disclosed in US. Pat. No. 2,647,049 to Edwin H. Land.

As examples of useful image-receiving materials, mention may be made of nylon, e.g., N-methoxymethylpolyhexamethylene adipamide, polyvinyl alcohol, and gelatin, particularly polyvinyl alcohol or gelatin containing a dye-mordant such as poly-4-vinylpyridine. The image-receiving element also may contain a development restrainer, e.g., l-phenyl-5-mercaptotetrazole, as disclosed in US. Pat. No. 3,265,498 issued Aug. 9, 1966 to Howard G. Rogers and Harriet W. Lutes.

The dye developers herein set forth are also useful in the formation of colored images in accordance with the photographic products and processes described and claimed in US. Pat. No. 2,968,554 issued to Edwin H. Land on Jan. 17, I961.

The novel compounds herein disclosed are also suitable for use as dyes for textile fibers. such as nylon.

In the preceding portions of the specification, the expression color has been frequently used. This expression is intended to include the use of a plurality of colors to obtain black, as well as the use of a single black dye developer.

-z i. .L wherein it is provided that of the 16 R substituents present on the phthalocyanine ring at least three and no more than four are R groups, there being no more than one R group on any one benzene ring, the remaining R substituents being hydrogen where R is wherein D is an alkylene group of from l-6 carbon atoms inclusive, X is hydrogen or an alkyl group having from 1-6 carbon atoms inclusive, Q is a disubstituted phenyl silver halide developing agent chosen from the group consisting of on l vHz oH 1 IH1 Q, Q or 1 I OH Wmli iaJS L. W on and M is a metal selected from the group consisting of cobalt, nickel, copper, chromium, magnesium and zinc.

2. A compound of the formula:

and D is an alkylene radical having from 1-6 carbon atoms inclusive, X is hydrogen or an alkyl group having from l-6 carbon atoms inclusive, Q is a disubstituted phenyl silver halide developing agent chosen from the group consisting of NH: NHe

H OH

I l l O Q Q or l l or; NH: NH: on

and M is a metal selected from the group consisting of cobalt, nickel, copper, chromium, magnesiumand zinc.

3. A compound of claim 2 wherein M is copper.

4. A compound of the formula:

wherein each R is on It 1 R=SOQI1ICIICII1 l on m 6. A compound of claim 4 of the formula:

N a l NCu-N\ l w/ l 0 on H I 3 R=SO;I1ICHCH:

I OH

7. A compound of claim 4 of the formula:

N=6 N H R N l a l N u-N I I 1, T

N=/ C N C;

OH CH3 l R=-SO2I I-CHCHz 

1. A COMPOUND OF THE FORMULA
 2. A compound of the formula:
 3. A compound of claim 2 wherein M is copper.
 4. A compound of the formula:
 5. A compound of claim 4 of the formula:
 6. A compound of claim 4 of the formula:
 7. A compound of claim 4 of the formula: 